Mono-azo dye



Patented May 19, 1931 UNETED STATES PATENT OFFICE OF WIESDOBF-ON-TI-ZE-RHINE, RUDOLF KNOCI-IE, OF LEVER- KTJ'SEN-ON-IHE-RI-IINE, AND PAUL VIE-GK, OF DESSAUwANHLALT, GERMANY, AS-

SIGNORS TO GENERAL ANILINE WORKS, INC., OF NEW YORK, Y., A CORPORATION OF DELAWABE- I MONO-AZO DYE No Drawing. Application filed. December ZO, 1927, Serial No. 241,448, and in Germany De'cember23, i926.

The present invention relates m me new azo dyestuffs of the general formula:

V Z Y wherein R represents a benzene or :naphthalene nucleus, X a nitro group, standing in paraosition tothe azo group, Y represents H or -CH S0 11, Z represents I hydrogen, alkoxy ora su'lfonicacid group, 6

represents hydrogen or a sulfonic acid group and a represents hydrogenyora'carboxylic I 7 acid group.

. Z Y V lam-n x wherein It represents a benzene or naphthalene nucleus, X a nitro group standing in para-position to the amino group, Y, represents SO H or *GH -SO H.and Zihydrogen, alkoxy or a sulfonic acid'group and coupling the diazo compound thus obtained with 3 a compound of the general formula: I p

wherein Y) represents hydrogen or a sulfonic acid group and a represents hydrogen or a carboxylic acid group. Thenew dyestuffs are very stable in spite of the free hydroxyl 40 group contained in their nucleus; They dye wool violet to blue-to blackshades. In so far as the new dyestuffs only contain one sulfonic group which is moreover'present in the diazo component, they dye acetate silk in clear fast shades. l

d jaminonaphthalene are formed.

' Upon treatment with stannous chloride and hydrochloric acid an aromatic para dialnine and l-amine-Q-K4 hydroxyphenyll.

Thefollowingexamples wi invention .Ewample 1.,T

ll illustrateour e diazo compound ob tained from 235 parts by. weight of the am monium salt of -nitro-l-aminobenzene 2-sulfonic acid is filtered ofi', suspended inglacial acetic acid and added in the cold, to a solution of 235 parts by'weight-of 4-hydroXyphenyl-Q aminonaphthalene in glacialacetic acid; the. coupling iis completed bythe addi-- tion, of sodium acetate. The resulting dye-f stuff having in its free.'- state the following formula is filtered, pressed and dried; It dyes wool in very powerful-bluish black even shades, possessing very good fastnessproperties in regard tolight, fulling, boiling with acid and steam pressing. Acetatesilkis dyed in violet blue shades. v

In the above example, the 4-hydroxyphenyl-2-aminonaphthalene can be replaced carboxylic acid.

EmampZe-j2.342 parts by weight/of the by lhydr'oxyphenyl-Q-aminonaphthalene-3 of l-hydroxyphenyl-2-aminonaphthalene in glacial acetic acid in the cold. The coupling is completed by the addition of sodium acetate; the resulting dyestuif having in its free state the following formula:

. BEEN- so3n +3 soan fin

is filtered and dried. It dyes wool in very powerful even bluish black shades of good fastness to light and fulliiig. 7

Instead of -nitraniline-Q.5-disulfonic acid 2-inethoxy-4-nitraniline-6-sulfonic acid can beemployed. g

If the 4-nitraniline-2.5-disulfonic acid in the above example is replaced byx2 l-9 parts by weight of the ammonium salt of 5-nitro- 2-aminobenzyl-(ii-sulfonic acid, a dyestuff is obtained, which dyes wool very powerful violet black shades of good fastness to light and fulling.

Ewample 3- 290 parts by Weight of the sodium salt of l-nitro-I-aminonaphthalene- 5-sulfonic acid are dissolved in water, a solution of 69 parts by weight of sodium nitrite in water is added thereto, and the whole is acidified with hydrochloricacid, stirringthe while. The diazo compound,,which is precipitated, is filtered off, suspended in glacial acetic acid and added in the cold to a solution of 235 parts by weight of l-hydroxyphenyl-2aminonaphthalene in glacial acetic acid. The coupling is completed by the addition of sodium acetate. The resulting dyestuff having in its free state the following formula: V

SfhHl tn is filtered and dried. It dyes wool very powerful even violet black shades of good fastness to light, fulling and steam pressing.

In this example, the l-nitro-l-aminonaphthalene-5-sulfonic acid can be replaced, among vothers, by; l-iiitro-l-aminonaphthalene-G-sulfonic acid.

In the following table several dyestufis are set out together with their respective shades on wool Dyestuil from Shade on wool 4 nitraniline 2 sulfonic 4-hydroxypheiiyl 2 blue-black ac d. aminonaphthalene. 4 n traniline 2 sulfonic 4-hydioxyphenyl 2 marine-blue acid aminonaphtlialenep 3-cai'boxy1ic acid 4 n tianiline 2 sulfonic 4-hydroxyphenyl 2 reddish blue acid aminonaphtlialene- 7-suli0nic acid 4 n traniline 2 sulfonic 4 -hydroxypheny1 2 bluish violet acid aininonaphthalene- 3-sulfoi1ic acid 2-1116thOXY-l-DltI'aI'llllI'lG-G- 4-liydi'0xyplienyl 2 violet sulfonic acid aniinonaplithaleno fi-nitro-Z-aminobenzyl-w- 4-liydroxyplienyl 7 2 violet sulfonic acid aminonaphthalene 5nitro -2-aminobenzy1-w- 4-hydroxyplieny1 2 violet sulfonic acid aminonaphthalene- 3-carboxy1ic acid 5-niti'o-2-aminobenzylw- 4-hydr0xyplienyl 2 violet sulfonic acid aminonaphtlialene- 7-sulionic acid 4 iiiti'aniline 2.5 disul- 4-hydroxypl1eny1 2 blue-black fonic acid aminonaplithalene 4-nitr0-1- aminonaplitha- 4-hy lro'xyphenyl 2 violet black lenc5-sulfonic acid aminonaplithalene 4-nitro1 aminonaphtha- 4-hydroxyphenyl 2 blue-black lene-6-si11fonic acid aminonaplithalene e claim v 1. As a new product the 'mono azo dyestuff having in its free form the formula:

being a dark powder, soluble in water and dyeing wool very powerful violet black shades of good fastness to light, fulling and steam pressing, and yielding upon treatment with stannous chloride and hydrochloric acid 1.l-phenylene-diamine sulfonic acid and 1- amino 2- (i T hydroXy -phenyl) =-ami11o-naphthalene. Y

2. As new products the mono azo-dyestuifs of the general formula: y

wherein R represents a benzene or naphthalene nucleus, X a nitro group standing in V para-position to the azo group, Y represents SO H or CH SO H, Z represents hydrogen, alkoXy' or a sulfonic acid group, 6 represents hydrogen or a sulfonic acid group and a represents hydrogen or a carboxylic acid group.

3. As new products the mono-azo-dye-. 'stu-fl's of the general formula:

rvherein Y represents S 11 or' CH SO H and Z represents hydrogen, alkoxy or a su1-. 'fonic acid group.

In testimony whereof vWe have hereuntq 

